Azo pigments containing pyrazoloquinazolone radicals

ABSTRACT

Azo compounds of the formula: ##STR1## wherein D is a radical of the formula: ##STR2## where Y 1  is acylamino, hydrogen, chlorine, bromine, nitro, cyano, carboxylic acid or ester, trifluoromethyl, alkoxy, methylsulfonyl, and substituted or substituted carbamyl or sulfamyl, phenylcarbonyl, naphthylcarbonyl, pyridylcarbonyl, oxodiazolyl, quinazolonyl phthalazinonyl, phenylazo, naphthylazo, or pyridylazo, 
     Y 2  is hydrogen, chlorine or bromine, 
     Y 4  is hydrogen or chlorine, 
     and wherein D is free from complex forming hydroxy or carboxy; R is hydrogen, phenyl, naphthyl or pyridyl and X is alkyl or a carboxylic acid alkyl ester, or is phenyl, naphthyl or pyridyl, or acylamino, can be used as pigments for coloring surface coatings, printing inks or plastics.

This is a division of application Ser. No. 083,327 filed Oct. 10, 1979, now U.S. Pat. No. 4,294,755.

BACKGROUND OF THE INVENTION SUMMARY OF THE INVENTION

The present invention provides compounds of the general formula I ##STR3## where D is the radical of a diazo compound of the aniline series which is free from complex-forming hydroxyl and carboxyl groups, R is hydrogen or an aromatic radical, X is alkyl, a carboxylic acid ester group, unsubstitued or substituted aryl or acylamino, and the ring A may be substituted but is free from SO₃ H groups.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Preferred compounds according to the invention have the general formula Ia ##STR4## where D, n and R have the stated meanings, R¹ is hydrogen, fluorine, chlorine, bromine, nitro, C₁ -C₄ -alkyl, trifluoromethyl, methoxy, ethoxy, aryloxy, carboxyl, a carboxylic acid ester group, unsubstituted or substituted carbamyl or sulfamyl, a sulfonic acid aryl ester group, arylsulfonyl, cyano, acylamino or phenyl, R² is hydrogen, chlorine or bromine, R³ and R⁴ are hydrogen, chlorine or bromine or together are a fused ring and X is hydroxyl, methyl, a carboxylic acid ester group, unsubstituted or substituted aryl or acylamino.

The radicals D are in the main derived from the aniline, aminoanthraquinone or aminophthalimide series or from tetraazo components. D-NH₂ may for example correspond to any of the following general formulae: ##STR5## where the radicals Y independently of one another are hydrogen, chlorine, bromine or acylamino, Y¹ is hydrogen, chlorine, bromine, nitro, cyano, a carboxylic acid ester group, trifluoromethyl, alkoxy, methylsulfonyl, unsubstituted or substituted carbamyl or sulfamyl, unsubstituted or substituted arylcarbonyl, oxdiazolyl, quinazolonyl, phthalazinonyl or arylazo, Y² is hydrogen, chlorine, bromine, nitro, cyano, a carboxylic acid ester group or unsubstituted or substituted oxdiazolyl, Y³ is hydrogen, chlorine or bromine, Y⁴ is hydrogen, chlorine, bromine or methyl, Y⁵ is hydrogen, chlorine, bromine, methyl or cyano and Y⁶ is hydrogen or unsubstituted or substituted phenyl or benzylamino.

Tetraazo components correspond to the general formula

    H.sub.2 N-D-NH.sub.2

where D is, for example, ##STR6## and Z is a direct bond, SO₂, NH, CO, SO₂ NH, CONH, NHCONH or NHCOCONH. The rings B may in addition be substituted by chlorine, bromine, methyl, nitro or methoxy.

Examples of carboxylic acid esters groups R¹, Y¹ and Y² are COOCH₃, COOC₂ H₅, COOC₃ H₇, COOC₄ H₉, ##STR7## COOC₆ H₅, COOC₂ H₄ OCH₃ or COOCH₂ C₆ H₅ and examples of carboxylic acid ester groups X are COOCH₃ and COOC₂ H₅.

Examples of amine radicals which may be present in unsubstituted or substituted carbamyl and sulfamyl radicals R¹ and Y¹ are:

NH₂, NHCH₃, NHC₂ H₅, NHC₃ H₇, NHC₄ H₉, ##STR8## NHCH₂ C₆ H₅, NHC₆ H₄ Cl, NHC₆ H₃ Cl₂, NHC₆ H₂ Cl₃, NHC₆ H₄ Br, NHC₆ H₄ OCH₃, NHC₆ H₄ OC₂ H₅, NHC₆ H₃ ClOCH₃, NHC₆ H₄ NHCOCH₃, NHC₆ H₄ NHCOC₆ H₅, NHNHCOC₆ H₅, NHNHCOC₆ H₄ Cl, NHNHCOC₆ H₄ CH₃, NHC₆ H₃ ClCH₃, NHC₆ H₂ Cl₂ OCH₃ and NHC₆ H₂ Cl₂ CH₃.

Examples of sulfonic acid aryl ester groups R¹ are: SO₂ OC₆ H₅, SO₂ OC₆ H₄ CH₃, SO₂ OC₆ H₄ Cl, SO₂ OC₆ H₄ Br, SO₂ OC₆ H₄ OCH₃, SO₂ OC₆ H₄ NHCOCH₃ and SO₂ OC₆ H₃ Cl₂.

Within the scope of the general definition, examples of heterocyclic radicals Y¹ and Y² are: ##STR9## where T is an unsubstituted or substituted aromatic radical.

Examples of acylamino radicals R¹, X and Y¹ are: NHCOCH₃, NHCOC₂ H₅, NHCOC₃ H₇, NHCOC₆ H₅, NHCOC₆ H₄ Cl, NHCOC₆ H₃ Cl₂, NHCOC₆ H₄ Br, NHCOC₆ H₄ OCH₃, NHCOC₁₀ H₇, NHCONH₂, NHCONHC₆ H₅, NHCOCONH₆ H₅, ##STR10## acylamino radicals Y are NHCOCH₃, NHCOC₆ H₅ and NHCOC₆ H₄ Cl.

Examples of radicals R and T are phenyl, naphthyl or pyridyl which may or may not be substituted by chlorine, bromine, nitro, methyl, methoxy or ethoxy; R, but not T, may furthermore be hydrogen. Specific examples are: 2-, 3- and 4-chlorophenyl, 2,4-, 2,5- and 3,5-dichlorophenyl, 2,4,5-trichlorophenyl, 2-, 3- and 4-bromophenyl, 2,5-dibromophenyl, 2- and 4-methoxyphenyl, 2- and 4-tolyl, 2,3-, 2,4- and 3,4-dimethylphenyl, 1- and 2-naphthyl, 4-chloro-1-naphthyl and 3-pyridyl.

A compound of the formula I may be prepared by reacting a diazonium compound of an amine of the formula DNH₂ or H₂ N-D-NH₂ with a coupling component of the formula ##STR11## where X is preferably hydroxyl or acylamino, if R is not hydrogen.

The coupling components are known from the literature or may be prepared by methods similar to those described in the literature. Details of suitable methods of performing the reactions may be found in the Examples, where parts and percentages are by weight. Temperatures are given in degrees centigrade.

The compounds of the formula I range from yellow to red and may be used as disperse dyes or as pigments, depending on the substituents. The pigments are frequently distinguished by great brilliance, high scattering power and excellent lightfastness and fastness to weathering, and may be used for coloring surface coatings, printing inks, plastics and plastic dispersions.

The pigments are not always obtained in the optimum physical form for a particular use. However, they can be converted to the most appropriate form by conventional methods, such as milling with salt, reprecipitation from sulfuric acid and/or heating in water or a solvent, in the presence or absence of wetting agents, dispersants and/or a grinding medium.

Compounds of the formula I particularly suitable for use as pigments are those which carry electron-attracting groups, such as NO₂, CN, COOR, --COAryl or heterocyclic radicals in the diazo component in the o-position to the azo bridge, or have an arylazo group in the p-position in the diazo component.

Compounds of particular importance are those of the formula Ib ##STR12## where D is the radical of a diazo component which is free from complex-forming hydroxyl and carboxyl groups and from ionic groups, and R¹ to R⁴ and X have the stated meanings. Preferably, X is methyl, or phenyl which is unsubstituted or substituted by chlorine, bromine, methyl, nitro or methoxy.

Preferably, D is substituted phenyl or anthraquinonyl and R¹ to R⁴ are hydrogen, chlorine, bromine, a carboxylic acid ester group or unsubstituted or substituted carbamyl or sulfamyl.

The preferred pigments, in the appropriate physical form, very frequently have very good fastness to weathering and combine high scattering power with a brilliant pure shade. They are therefore particularly suitable as an equivalent substitute for, eg., chromate pigments or molybdate pigments, for which purpose they may also be used as a mixture with inorganic pigments of the spinel type.

EXAMPLE 1

8.6 parts of 2-nitro-4-chloroaniline are dissolved in 10 parts of dimethylformamide, the solution is poured into a mixture of 20 parts of concentrated hydrochloric acid, 50 parts of water and 50 parts of ice, and diazotization is carried out by dropwise addition of a solution of 3.5 parts of sodium nitrite in 10 parts of water at 0°-5° C. After 1 hour, excess nitrite is destroyed with amidosulfonic acid, the solution is clarified by filtration, the pH is brought to 5 by adding sodium acetate and a suspension of 10 parts of 2-methylpyrazolo[5,1b]quinazolone, 100 parts of isobutanol and 8 parts of 50% strength aqueous sodium hydroxide solution is added dropwise in the course of one hour. The mixture is stirred for 1 hour at 0°-5° C. and 1 hour at 50° C. The colorant is then filtered off, washed with hot water and then with methanol, dried, stirred for 2 hours with 80 parts of dimethylformamide at 80° C., again filtered, washed with methanol, dried and milled. 15 parts of an orange crystalline powder of the formula ##STR13## are obtained.

The colorants identified in Table 1 by their diazo components and coupling components are obtained similarly.

                                      TABLE 1                                      __________________________________________________________________________          Diazo          Coupling                                                   Example                                                                             component      component            Hue                                   __________________________________________________________________________           ##STR14##                                                                                     ##STR15##           orange                                3    "                                                                                              ##STR16##           "                                     4    "                                                                                              ##STR17##           "                                     5    "                                                                                              ##STR18##           "                                     6    "                                                                                              ##STR19##           "                                     7    "                                                                                              ##STR20##           red                                   8    "                                                                                              ##STR21##           "                                     9    "                                                                                              ##STR22##           orange                                10   "                                                                                              ##STR23##           "                                     11                                                                                   ##STR24##                                                                                     ##STR25##           red                                   12   "                                                                                              ##STR26##           bluish red                            13   "                                                                                              ##STR27##           red                                   14   "                                                                                              ##STR28##           "                                     15                                                                                   ##STR29##                                                                                     ##STR30##           "                                     16   "                                                                                              ##STR31##           "                                     17   "                                                                                              ##STR32##           "                                     18                                                                                   ##STR33##                                                                                     ##STR34##           "                                     19   "                                                                                              ##STR35##           "                                     20   "                                                                                              ##STR36##           "                                     21   "                                                                                              ##STR37##           "                                     22                                                                                   ##STR38##                                                                                     ##STR39##           yellow                                23                                                                                   ##STR40##     "                    red                                   24                                                                                   ##STR41##     "                    yellow                                25                                                                                   ##STR42##     "                    red                                   26   "                                                                                              ##STR43##           "                                     __________________________________________________________________________

EXAMPLE 27

22.4 parts of 1-aminoanthraquinone are introduced into a mixture of 46 parts of 96% strength sulfuric acid and 34 parts of 40% strength nitrosylsulfuric acid at a rate such that the temperature does not exceed 40° C., and the mixture is then stirred for two hours at 40° C. Thereafter the solution is stirred into 300 parts of ice and water, and the diazonium sulfate which has crystallized out is filtered off, washed with ice water and stirred into 400 parts of water. The pH is brought to 4-5 with sodium acetate and after having added 10 parts of glacial acetic acid a suspension prepared by stirring 27 parts of 5,7-dichloro-2-methyl-pyrazolo[5,1b]quinazolone and 10 parts of 50% strength aqueous sodium hydroxide solution with 300 parts of isobutanol at 90° C. is added dropwise at 40° C. To complete the coupling, the mixture is stirred for 2 hours at 95° C., after which it is filtered hot, the filter residue is washed with water and then with methanol and the colorant thus obtained is dried and milled. 44 parts of a red powder are obtained; this is stirred with 300 parts of dimethylformamide for 2 hours at 80° C., filtered off hot, washed with dimethylformamide and then with methanol, dried and milled. A red crystalline powder of the formula ##STR44## is obtained.

The colorants identified in Table 2 by their diazo components and coupling components are obtained similarly.

                                      TABLE 2                                      __________________________________________________________________________     Example                                                                              Diazo component       Coupling component             Hue                 __________________________________________________________________________     28                                                                                    ##STR45##                                                                                            ##STR46##                     red                 29    "                                                                                                     ##STR47##                     red                 30    "                                                                                                     ##STR48##                     red                 31    "                                                                                                     ##STR49##                     red                 32    "                                                                                                     ##STR50##                     red                 33    "                                                                                                     ##STR51##                     red                 34                                                                                    ##STR52##                                                                                            ##STR53##                     red                 35    "                                                                                                     ##STR54##                     orange              36    "                                                                                                     ##STR55##                     red                 37    "                                                                                                     ##STR56##                     red                 38    "                                                                                                     ##STR57##                     red                 39    "                                                                                                     ##STR58##                     red                 40                                                                                    ##STR59##                                                                                            ##STR60##                     red                 41    "                                                                                                     ##STR61##                     red                 42    "                                                                                                     ##STR62##                     red                 43    "                                                                                                     ##STR63##                     red                 44    "                                                                                                     ##STR64##                     red                 45    "                                                                                                     ##STR65##                     red                 46    "                                                                                                     ##STR66##                     red                 47                                                                                    ##STR67##                                                                                            ##STR68##                     red                 48    "                                                                                                     ##STR69##                     red                 49    "                                                                                                     ##STR70##                     red                 50    "                                                                                                     ##STR71##                     red                 51    "                                                                                                     ##STR72##                     reddish brown       52    "                                                                                                     ##STR73##                     reddish brown       53    "                                                                                                     ##STR74##                     reddish brown       54    "                                                                                                     ##STR75##                     brown               55    "                                                                                                     ##STR76##                     red                 56    "                                                                                                     ##STR77##                     red                 57    "                                                                                                     ##STR78##                     red                 58    "                                                                                                     ##STR79##                     red                 59    "                                                                                                     ##STR80##                     red                 60    "                                                                                                     ##STR81##                     red                 61    "                                                                                                     ##STR82##                     red                 62    "                                                                                                     ##STR83##                     red                 63    "                                                                                                     ##STR84##                     red                 64    "                                                                                                     ##STR85##                     red                 65    "                                                                                                     ##STR86##                     red                 66    "                                                                                                     ##STR87##                     red                 67    "                                                                                                     ##STR88##                     red                 68    "                                                                                                     ##STR89##                     red                 69    "                                                                                                     ##STR90##                     red                 70    "                                                                                                     ##STR91##                     red                 71    "                                                                                                     ##STR92##                     red                 72    "                                                                                                     ##STR93##                     red                 73    "                                                                                                     ##STR94##                     red                 74    "                                                                                                     ##STR95##                     red                 75    "                                                                                                     ##STR96##                     orange              76    "                                                                                                     ##STR97##                     orange              77    "                                                                                                     ##STR98##                     orange              78    "                                                                                                     ##STR99##                     orange              79    "                                                                                                     ##STR100##                    red                 80    "                                                                                                     ##STR101##                    orange              81    "                                                                                                     ##STR102##                    red                 82    "                                                                                                     ##STR103##                    red                 83    "                                                                                                     ##STR104##                    red                 84    "                                                                                                     ##STR105##                    red                 85    "                                                                                                     ##STR106##                    red                 86    "                                                                                                     ##STR107##                    red                 87    "                                                                                                     ##STR108##                    red                 88    "                                                                                                     ##STR109##                    red                 89    "                                                                                                     ##STR110##                    orange              90    "                                                                                                     ##STR111##                    red                 91    "                                                                                                     ##STR112##                    red                 92    "                                                                                                     ##STR113##                    red                 93    "                                                                                                     ##STR114##                    red                 94    "                                                                                                     ##STR115##                    red                 95    "                                                                                                     ##STR116##                    red                 96                                                                                    ##STR117##                                                                                           ##STR118##                    red                 97    "                                                                                                     ##STR119##                    red                 98    "                                                                                                     ##STR120##                    red                 99    "                                                                                                     ##STR121##                    red                 100   "                                                                                                     ##STR122##                    reddish brown       101   "                                                                                                     ##STR123##                    red                 102   "                                                                                                     ##STR124##                    red                 103   "                                                                                                     ##STR125##                    red                 104   "                                                                                                     ##STR126##                    orange              105   "                                                                                                     ##STR127##                    orange              106   "                                                                                                     ##STR128##                    orange              107   "                                                                                                     ##STR129##                    orange              108                                                                                   ##STR130##                                                                                           ##STR131##                    reddish brown       109                                                                                   ##STR132##                                                                                           ##STR133##                    red                 110   "                                                                                                     ##STR134##                    red                 111   "                                                                                                     ##STR135##                    red                 112   "                                                                                                     ##STR136##                    reddish brown       113   "                                                                                                     ##STR137##                    reddish brown       114   "                                                                                                     ##STR138##                    red                 115   "                                                                                                     ##STR139##                    red                 116   "                                                                                                     ##STR140##                    red                 117                                                                                   ##STR141##                                                                                           ##STR142##                    red                 118   "                                                                                                     ##STR143##                    red                 119   "                                                                                                     ##STR144##                    red                 120   "                                                                                                     ##STR145##                    red                 121   "                                                                                                     ##STR146##                    orange              122   "                                                                                                     ##STR147##                    red                 123   "                                                                                                     ##STR148##                    red                 124   "                                                                                                     ##STR149##                    red                 125   "                                                                                                     ##STR150##                    red                 126                                                                                   ##STR151##                                                                                           ##STR152##                    red                 127   "                                                                                                     ##STR153##                    red                 128   "                                                                                                     ##STR154##                    red                 129   "                                                                                                     ##STR155##                    orange              130   "                                                                                                     ##STR156##                    orange              131   "                                                                                                     ##STR157##                    red                 132   "                                                                                                     ##STR158##                    reddish brown       133   "                                                                                                     ##STR159##                    red                 134   "                                                                                                     ##STR160##                    red                 135                                                                                   ##STR161##                                                                                           ##STR162##                    yellow              136   "                                                                                                     ##STR163##                    orange              137                                                                                   ##STR164##                                                                                           ##STR165##                    red                 138   "                                                                                                     ##STR166##                    red                 139   "                                                                                                     ##STR167##                    red                 140   "                                                                                                     ##STR168##                    red                 141   "                                                                                                     ##STR169##                    reddish brown       142   "                                                                                                     ##STR170##                    red                 143   "                                                                                                     ##STR171##                    red                 144   "                                                                                                     ##STR172##                    red                 145   "                                                                                                     ##STR173##                    reddish brown       146   "                                                                                                     ##STR174##                    red                 147   "                                                                                                     ##STR175##                    red                 148   "                                                                                                     ##STR176##                    red                 149   "                                                                                                     ##STR177##                    red                 150   "                                                                                                     ##STR178##                    red                 151   "                                                                                                     ##STR179##                    red                 152   "                                                                                                     ##STR180##                    red                 __________________________________________________________________________

EXAMPLE 153

19.6 parts of 3-chloro-6-amino-phthalimide, in a mixture of 150 parts of glacial acetic acid, 50 parts of propionic acid and 30 parts of concentrated hydrochloric acid, are diazotized, at 5° C., with 7 parts of sodium nitrite. After 2 hours, the excess nitrite is destroyed with amidosulfonic acid and the pH is brought to 4-5 by adding solid sodium acetate. 20 parts of 2-methylpyrazolo[5,1b]quinazolone are stirred with 200 parts of isobutanol and 10 parts of 50% strength aqueous sodium hydroxide solution for 2 hours at 90° C., and the mixture is cooled to 20° C. and then added dropwise in the course of 1 hour to the diazo solution. The mixture is stirred for 1 hour at 20° C. and 2 hours at 60° C. and is then filtered, and the filter residue is washed with glacial acetic acid, then with water and thereafter with methanol, and is dried. 36 parts of crude product are obtained; this is stirred with 360 parts of dimethylformamide for 2 hours at 100° C., filtered off, washed with methanol, dried and milled. 35 parts of a yellow crystalline powder of the formula ##STR181## are obtained.

The colorants identified in Table 3 by their diazo components and coupling components are obtained similarly.

                                      TABLE 3                                      __________________________________________________________________________          Diazo                 Coupling                                            Example                                                                             component             component                 Hue                       __________________________________________________________________________     154                                                                                  ##STR182##                                                                                           ##STR183##               yellow                    155                                                                                  ##STR184##             "                       yellow                    156                                                                                  ##STR185##             "                       yellow                    157                                                                                  ##STR186##             "                       yellowish orange          158                                                                                  ##STR187##             "                       reddish brown             159                                                                                  ##STR188##                                                                                           ##STR189##               red                       160                                                                                  ##STR190##             "                       orange                    161                                                                                  ##STR191##                                                                                           ##STR192##               red                       162                                                                                  ##STR193##                                                                                           ##STR194##               yellowish orange          163                                                                                  ##STR195##             "                       yellow                    164                                                                                  ##STR196##                                                                                           ##STR197##                "                        165                                                                                  ##STR198##                                                                                           ##STR199##               red                       166    "                                                                                                   ##STR200##                "                        167    "                                                                                                   ##STR201##                "                        168                                                                                  ##STR202##                                                                                           ##STR203##               orange red                169                                                                                  ##STR204##                                                                                           ##STR205##               orange                    170    "                                                                                                   ##STR206##               red                       171    "                                                                                                   ##STR207##                 "                       172                                                                                  ##STR208##                                                                                           ##STR209##                "                        173    "                                                                                                   ##STR210##                "                        174    "                                                                                                   ##STR211##                "                        175    "                                                                                                   ##STR212##                "                        176    "                                                                                                   ##STR213##                "                        177    "                                                                                                   ##STR214##                "                        178    "                                                                                                   ##STR215##                "                        179    "                                                                                                   ##STR216##                "                        180    "                                                                                                   ##STR217##                "                        181    "                                                                                                   ##STR218##                "                        182    "                                                                                                   ##STR219##                "                        183    "                                                                                                   ##STR220##                 "                       __________________________________________________________________________

EXAMPLE 184

35.4 parts of 7-(N-phenylsulfamyl)-2-methyl-pyrazolo[5,1-b]-quinazolone, 20 parts of sodium hydroxide and 6 parts of an alkylnaphthalenesulfonate are stirred into 300 parts of water, a suspension of 1-anthraquinone-diazonium sulfate, as described in Example 27, is added and the mixture is stirred for 1 hour. After adding 30 parts of glacial acetic acid, the batch is stirred for 1 hour at room temperature, 1 hour at 40° C., 1 hour at 60° C. and 2 hours under reflux, and the product is filtered off hot and washed with water. The moist filter cake is introduced into 310 parts of molten phenol and this mixture is stirred for 4 hours at 140° C. during which water distils off. After having added 400 parts of methanol at 50° C., the mixture is filtered and the filter residue is washed with methanol until the filtrate is clear, and is then dried and milled. 57.5 parts of a brilliant red pigment powder, of the same formula as in Example 48, but having improved technological properties, are obtained.

The pigments which have the general formula shown below and are characterized in Table 4 by the meanings of D, X and R¹ are obtained similarly.

                                      TABLE 4                                      __________________________________________________________________________      ##STR221##                                                                    Example                                                                             D          R.sup.1           X    Hue                                     __________________________________________________________________________     185                                                                                  ##STR222##                                                                                ##STR223##       CH.sub.3                                                                            orange red                              186  "                                                                                          ##STR224##       "    red                                     187  "                                                                                          ##STR225##       "     "                                      188  "                                                                                          ##STR226##       "     "                                      189  "                                                                                          ##STR227##       "    orange                                  190  "                                                                                          ##STR228##       "    red                                     191  "                                                                                          ##STR229##       "    orange                                  192  "                                                                                          ##STR230##       "    orange red                              193  "                                                                                          ##STR231##       "    red                                     194  "                                                                                          ##STR232##       "     "                                      195  "                                                                                          ##STR233##       "     "                                      196  "                                                                                          ##STR234##       "     "                                      197  "                                                                                          ##STR235##       "     "                                      198  "                                                                                          ##STR236##       "     "                                      199  "                                                                                          ##STR237##       "     "                                      200  "                                                                                          ##STR238##       "     "                                      201  "                                                                                          ##STR239##       CH.sub.3                                                                             "                                      202  "                                                                                          ##STR240##       "     "                                      203  "                                                                                          ##STR241##       "    orange red                              204  "                                                                                          ##STR242##       "    red                                     205  "                                                                                          ##STR243##       "     "                                      206  "                                                                                          ##STR244##       "     "                                      207  "                                                                                          ##STR245##       "     "                                      208  "                                                                                          ##STR246##       "     "                                      209  "                                                                                          ##STR247##       CH.sub.3                                                                             "                                      210  "                                                                                          ##STR248##       "     "                                      211  "                                                                                          ##STR249##       "     "                                      212  "                                                                                          ##STR250##       "     "                                      213  "                                                                                          ##STR251##       "     "                                      214  "                                                                                          ##STR252##       "     "                                      215  "                                                                                          ##STR253##       "    orange                                  216  "                                                                                          ##STR254##       "    red                                     217  "                                                                                          ##STR255##       "     "                                      218  "                                                                                          ##STR256##       "     "                                      219  "                                                                                          ##STR257##       "     "                                      220  "                                                                                          ##STR258##       "     "                                      221  "                                                                                          ##STR259##       "     "                                      222  "                                                                                          ##STR260##       "     "                                      223  "                                                                                          ##STR261##       "     "                                      224  "                                                                                          ##STR262##       "    orange                                  225  "                                                                                          ##STR263##                                                                                       ##STR264##                                                                         red                                     226  "                                                                                          ##STR265##       "     "                                      227  "                                                                                          ##STR266##       "     "                                      228  "                                                                                          ##STR267##       "     "                                      229  "                                                                                          ##STR268##       "     "                                      230  "                                                                                          ##STR269##       "     "                                      231  "                                                                                          ##STR270##       "     "                                      232  "                                                                                          ##STR271##       "     "                                      233  "                                                                                          ##STR272##       "     "                                      234  "                                                                                          ##STR273##       "     "                                      235                                                                                  ##STR274##                                                                                ##STR275##       CH.sub.3                                                                             "                                      236  "                                                                                          ##STR276##       "     "                                      237  "                                                                                          ##STR277##       "     "                                      238  "                                                                                          ##STR278##       "     "                                      239  "                                                                                          ##STR279##       "     "                                      240  "                                                                                          ##STR280##       "     "                                      241  "                                                                                          ##STR281##       "     "                                      242  "                                                                                          ##STR282##       "     "                                      243  "                                                                                          ##STR283##                                                                                       ##STR284##                                                                          "                                      244  "                                                                                          ##STR285##       "     "                                      245  "                                                                                          ##STR286##       "     "                                      246  "                                                                                          ##STR287##       "     "                                      247                                                                                  ##STR288##                                                                                ##STR289##       CH.sub.3                                                                             "                                      248  "                                                                                          ##STR290##       "     "                                      249  "                                                                                          ##STR291##       "     "                                      250  "                                                                                          ##STR292##       "     "                                      251  "                                                                                          ##STR293##       "     "                                      252  "                                                                                          ##STR294##                                                                                       ##STR295##                                                                          "                                      253  "                                                                                          ##STR296##       "     "                                      254                                                                                  ##STR297##                                                                                ##STR298##       CH.sub.3                                                                             "                                      255  "                                                                                          ##STR299##       "     "                                      256  "                                                                                          ##STR300##                                                                                       ##STR301##                                                                          "                                      __________________________________________________________________________

EXAMPLE 257

22.4 parts of 1-aminoanthraquinone and 30 parts of concentrated hydrochloric acid are stirred with 300 parts of glacial acetic acid for 1 hour at room temperature. 7.5 parts of sodium nitrite are then added in portions over 1 hour, and the mixture is stirred for a further 2 hours. To remove excess nitrite, urea is added, the mixture is buffered with 35 parts of anhydrous sodium acetate, and a suspension, prepared at 40° C., of 42 parts of 2-methyl-pyrazolo[5,1-b]-quinazolone-7-sulfonic acid 2',4'-dichlorophenyl ester and 10 parts of 50% strength aqueous sodium hydroxide solution in 400 parts of isobutanol is added dropwise over 1 hour. The mixture is stirred for 3 hours at 40° C., 1 hour at 60° C. and 2 hours at the reflux temperature and is filtered, and the product is washed with hot water and dried. The crude product is then stirred with 500 parts of dimethylformamide at 80° C. for 2 hours, filtered off, washed with methanol, dried and milled. 58 parts of a brilliant red powder of the formula ##STR302## are obtained.

The pigments of the general formula ##STR303## listed in Table 5 are obtained by a similar method.

                                      TABLE 5                                      __________________________________________________________________________     Example                                                                             D          R.sup.1       X    Hue                                         __________________________________________________________________________     258                                                                                  ##STR304##                                                                                ##STR305##   CH.sub.3                                                                            red                                         259  "                                                                                          ##STR306##   "    "                                           260  "                                                                                          ##STR307##   "    "                                           261  "                                                                                          ##STR308##   "    "                                           262  "                                                                                          ##STR309##   "    "                                           263  "                                                                                          ##STR310##   "    "                                           264  "                                                                                          ##STR311##   "    "                                           265  "                                                                                          ##STR312##   "    "                                           266  "                                                                                          ##STR313##   "    "                                           267  "                                                                                          ##STR314##   "    "                                           268  "                                                                                          ##STR315##   "    "                                           269  "                                                                                          ##STR316##   "    "                                           270  "                                                                                          ##STR317##   "    "                                           271  "                                                                                          ##STR318##   "    "                                           272  "                                                                                          ##STR319##   "    "                                           273  "                                                                                          ##STR320##                                                                                   ##STR321##                                                                         "                                           274  "                                                                                          ##STR322##   "    "                                           275  "                                                                                          ##STR323##   "    "                                           276  "                                                                                          ##STR324##   "    "                                           277  "                                                                                          ##STR325##   "    "                                           278  "                                                                                          ##STR326##   "    "                                           279  "                                                                                          ##STR327##   "    "                                           280  "                                                                                          ##STR328##   "    "                                           281                                                                                  ##STR329##                                                                                ##STR330##   CH.sub.3                                                                            "                                           282  "                                                                                          ##STR331##   "    "                                           283  "                                                                                          ##STR332##                                                                                   ##STR333##                                                                         "                                           284  "                                                                                          ##STR334##   "    "                                           285                                                                                  ##STR335##                                                                                ##STR336##   CH.sub.3                                                                            "                                           286  "                                                                                          ##STR337##   "    "                                           287  "                                                                                          ##STR338##   "    "                                           288  "                                                                                          ##STR339##                                                                                   ##STR340##                                                                         "                                           __________________________________________________________________________

USE EXAMPLE 1 10% strength full-shade baking finish on paper

(a) 30% strength full-shade paste

3 parts of the colorant of Example 27 and 7 parts of a varnish-like binder (for example Grinding Base 100S from Lawter Chemicals Inc., Chicago) are passed 6 times through a triple-roll mill under 10 bar pressure, to give a full-shade paste.

(b) 10% strength full-shade coating paste used for coloring

2 parts of the full-shade paste obtained in (a) are mixed with 4 parts of a binder mixture, comprising 1 part of an alkyd resin modified with soybean oil, 2 parts of an alkyd resin modified with synthetic fatty acid and 3 parts of a solvent-free melamine resin.

(c) Coloration process

Using a film coater, a 100 μm thick layer of the surface-coating paste obtained as described in (b) is applied to cardboard printed with a black bar and is baked for 45 minutes at 120° C. in a drying oven. A high-hiding and brilliant red coloration having excellent lightfastness and fastness to weathering is obtained.

USE EXAMPLE 2 1:20 reduction baking finish

(a) 30% strength white paste

42 parts of a binder, obtained by mixing 1 part of an alkyd resin modified with soybean oil and 2 parts of an alkyd resin modified with synthetic fatty acid are milled with 30 parts of titanium dioxide (rutile grade), 22 parts of a solvent-free melamine resin and 6 parts of a colloidal silica by passing 6 times through a triple-roll mill under 10 bar pressure, to give a 30% strength white paste.

(b) Surface-coating paste used for coloring 0.5 part of the 30% strength full-shade paste obtained as described in (1a) and 10 parts of the 30% strength white paste obtained as described in (2a) are mixed, and milled, on a millstone mill.

(c) Coloration process

Using a film coater, a 100 μm thick layer of the surface-coating paste (b) is applied to cardboard and baked for 45 minutes at 120° C. in a drying oven. A yellowish red coloration having excellent lightfastness and fastness to weathering is obtained.

USE EXAMPLE 3 Plasticized PVC (0.1% strength coloration)

0.05 part of the colorant obtained as described in Example 27 and 50 parts of a mixture itself prepared from 65 parts of PVC powder, 36 parts of di-ethylhexyl phthalate and 2 parts of dibutyl-tin bis-(hexyl thioglycolate), are homogenized for about 8 minutes on a mixing mill at 150°-160° C., and then converted to hides which are polished on a calender. Brilliant red hides having excellent lightfastness are obtained. If titanium dioxide is added during the compounding operation, yellowish red reductions having excellent light-fastness are obtained.

USE EXAMPLE 4 Rigid PVC (0.1% strength coloration)

0.1 part of colorant obtained as described in Example 27, 100 parts of PVC powder (suspension polymer or emulsion polymer) and 2 parts of dibutyl-tin bis-(hexyl thioglycolate) are homogenized in about 8 minutes at 150°-160° C. on a mixing mill. The hides obtained are pressed to form sheets on a platen press at 140° C. under about 0.4 kg/cm². Brilliant red pressed sheets having excellent lightfastness are obtained. If titanium dioxide is added during the compounding operation, yellowish red reductions having excellent light-fastness are obtained.

USE EXAMPLE 5 Printing ink

5 parts of the colorant obtained as described in Example 153, 30-40 parts of resin (for example rosin modified with a phenol-formaldehyde resin) and 65 parts of toluene are thoroughly mixed in a disperser. This gives a toluene-based gravure printing ink having good lightfastness and good tinctorial strength.

USE EXAMPLE 6 Plasticized PVC; 1:10 reduction

0.25 part of colorant, obtained as described in Example 184, 2.5 parts of titanium dioxide (rutile grade) and 50 parts of a mixture itself obtained from 65 parts of polyvinyl chloride powder, 36 parts of di-ethylhexyl phthalate and 2 parts of dibutyl-tin bis-(hexyl thioglycolate), are homogenized in about 8 minutes on a mixing mill at 150°-160° C., and then converted to hides which are polished on a calender. Brilliant red hides having excellent lightfastness and fastness to migration are obtained.

USE EXAMPLE 7 Polyethylene (0.05% strength coloration)

0.05 part of colorant obtained as described in Example 189 and 100 parts of high-pressure polyethylene powder are dry-blended in a drum mixer. The mixture is melted, and homogenized, on an extruder at a barrel temperature of 160°-200° C. The colored material is granulated by die-face cutting or by drawing strands which are cooled and granulated. The granules obtained are then injection-molded at 200° C. or compression-molded to various shapes on presses. Brilliant orange moldings having excellent lightfastness and heat stability are obtained. 

We claim:
 1. An azo compound of the formula ##STR341## wherein D is a radical of the formula ##STR342## where Y¹ is acylamino selected from the group consisting of NHCOCH₃, NHCOC₂ H₅, NHCOC₃ H₇, NHCOC6H₅, NHCOC₆ H₄ Cl, NHCOC₆ H₃ Cl₂, NHCOC₆ H₄ Br₁, NCOC₆ H₄ OCH₃, NHCOC₁₀ H₇, NHCONHC₆ H₅, ##STR343## Y¹ is hydrogen; chlorine; bromine, nitro; cyano, a carboxylic acid ester having an ester radical selected from the group consisting of C₁ -C₆ alkyl or alkoxy-alkyl, phenyl and benzyl; trifluoromethyl; alkoxy; methylsulfonyl; quinazolonyl; phthalazinonyl; phenylazo; naphthylazo; pyrodiylazo; or unsubstituted or substituted carbamyl or sulfamyl wherein the substituent radicals are selected from the group consisting of NH₂, NHCH₃, NHC₂ H₅, NHC₃ H₇, NHC₄ H₉, ##STR344## NHCH₂ C₆ H₅, NHC₆ H₄ Cl, NHC₆ H₃ Cl₂, NHC₆ H₂ Cl₃, NHC₆ H₄ Br, NHC₆ H₄ OCH₃, NHC₆ H₄ OC₂ H₅, NHC₆ H₃ ClOCH₃, NHC₆ H₄ NHCOCH₃, NHC₆ H₄ NHCOC₆ H₅, NHNHCOC₆ H₅, NHNHCOC₆ H₄ Cl, NHNHCOC6H₄ CH₃, NHC₆ H₃ ClCH₃, NHC₆ H₂ Cl₂ OCH₃ and NHC₆ H₂ Cl₂ CH₃ ;Y² is hydrogen, chlorine, bromine, nitro, cyano, a carboxylic acid ester having an ester radical selected from the group consisting of C₁ -C₆ alkyl or alkoxy-alkyl, phenyl and benzyl; or Y² is oxdiazolyl, Y³ is hydrogen, chlorine or bromine; Y⁴ is hydrogen or chlorine; and wherein D is free from complex-forming hydroxy or carboxy; R is hydrogen; X is alkyl, or a carboxylic acid alkyl ester having an alkyl ester radical selected from the group consisting of C₁ -C₆ alkyl or alkoxyalkyl, phenyl and benzyl; or X is phenyl, naphthyl or pyridyl which are unsubstituted or substituted by chlorine, bromine, nitro, methyl, methoxy or ethoxy; or X is acylamino selected from the group consisting of NHCOCH₃, NHOCOC₂ H₅, NHCOC₃ H₇, NHCOC₆ H₅, NHCOC₆ H₄ Cl, NHCOC₆ H₃ Cl₂, NHCOC₆ H₄ Br, NHCOC₆ H₄ OCH₃, NHCOC₁₀ H₇, NHCOHN₂, NHCONHC₆ H₅, ##STR345## and the ring A is substituted or unsubstituted, with the proviso that said ring A is free from SO₃ H groups.
 2. An azo compound of the formula: ##STR346## wherein D is a radical of the formula: ##STR347## where Y¹ is acylamino selected from the group consisting of NHCOCH₃, NHCOC₂ H₅, NHCOC₃ H₇, NHCOC₆ H₅, NHCOC₆ H₄ Cl, NHCOC₆ H₃ Cl₂, NHCOC₆ H₄ Br, NHCOC₆ H₄ OCH₃, NHCOC₁₀ H₇, NHCONH₂, NHCONHC₆ H₅ ; ##STR348## Y¹ is hydrogen; chlorine; bromine, nitro; cyano; a carboxylic acid alkyl ester having an alkyl radical selected from the group consisting of C₁ -C₆ alkyl or alkoxy alkyl, phenyl and benzyl; trifluoromethyl; alkoxy; methylsulfonyl; phenylcarbonyl; naphthylcarbonyol; pyridylcarbonyl; oxdiazolyl; quinazolonyl; phthalazinoyl; phenylazo; naphthylazo; pyridylazo; or unsbustituted or substituted carbamyl or sulfamyl wherein the substituent radicals are selected from the group consisting of NH₂, NHCH₃, NHC₂ H₅, NHC₃ H₇, NHC₄ H₉, ##STR349## NHCH₂ C₆ H₅, NHC₆ H₄ Cl, NHC₆ H₃ Cl₂, NHC₆ H₂ Cl₃, NHC₆ H₄ Br, NHC₆ H₄ OCH₃, NHC₆ H₄ OC₂ H₅, NHC₆ H₃ ClOCH₃, NHC₆ H₄ NHCOCH₃, NHC₆ H₄ NHCOC₆ H₅, NHNHCOC₆ H₅, NHNHCOC₆ H₄ Cl, NHNHCOC₆ H₄ CH₃, NHC₆ H₃ ClCH₃, NHC₆ H₂ Cl₂ OCH₃ and NHC₆ H₂ Cl₂ CH₃ ;Y² is hydrogen, chlorine, bromine, nitro, cyano, a carboxylic acid alkyl ester having an alkyl radical selected from the group consisting of C₁ -C₆ alkyl or alkoxy alkyl, phenyl and benzyl; or oxidazoly, Y³ is hydrogen, chlorine or bromine; Y⁴ is hydrogen, chlorine; and wherein D is free from complex-forming hydroxy or carboxy, R is hydrogen; R¹ is hydrogen, fluorine, chlorine, bromine, nitro, C₁ -C₄ alkyl, trifluoromethyl, methoxy, ethoxy, phenyloxy, pyridyloxy, naphthyloxy, carboxy, a carboxylic acid alkyl ester having an alkyl ester radical selected from the group consisting of C₁ -₆ alkyl or alkoxyalkyl, phenyl and benzyl; unsubstituted or substituted carbamyl or sulfamyl wherein the substituent radicals are selected from the group consisting of NH₂, NHCH₃, NHC₂ H₅, NHC₃ H₇, NHC₄ H₉, ##STR350## NHCH₂ C₆ H₅, NHC₆ H₄ Cl, NHC₆ H₃ Cl₂, NHC₆ H₂ Cl₃, NHC₆ H₄ Br, NHC₆ H₄ OCH₃, NHC₆ H₄ OC₂ H₅, NHC₆ H₃ ClOCH₃, NHC₆ H₄ NHCOCH₃, NHC₆ H₄ NHCOC₆ H₅, NHNHCOC₆ H₅, NHNHCOC₆ H₄ Cl, NHNHCOC₆ H₄ CH₃, NHC₆ H₃ ClCH₃, NHC₆ H₂ Cl₂ OCH₃ and NHC₆ H₂ Cl₂ CH₃ ; a sulfonic acid aryl ester group, arylsulfonyl, cyano, acylamino selected from the group consisting of NHCOCH₃, NHCOC₂ H₅, NHCOC₃ H₇, NHCOC₆ H₅, NHCOC₆ H₄ Cl, NHCOC₆ H₃ Cl₂, NHCOC₆ H₄ Br, NHCOC₆ H₄ OCH₃, NHCOC₁₀ H₇, NHCONH₂, NHCONHC₆ H₅, ##STR351## or R¹ is phenyl; R² is hydrogen, chlorine or bromine; R³ and R⁴ are hydrogen, chlorine or bromine; and X is methyl, a carboxylic acid alkyl ester having an alkyl ester radical selected from the group consisting of C₁ -C₆ alkyl or alkoxyalkyl, phenyl, and benzyl; or X is phenyl, naphthyl or pyridyl which is unsubstituted or substituted by chlorine, bromine, nitro, methyl, methoxy or ethoxy; or X is acylamino selected from the group consisting of NHCOCH₃, NHOCOC₂ H₅, NHCOC₃ H₇, NHCOC₆ H₅, NHCOC₆ H₄ Cl, NHCOC₆ H₃ Cl₂, NHCOC₆ H₄ Br, NHCOC₆ H₄ OCH₃, NHCOC₁₀ H₇, NHCONH₂, NHCONHC₆ H₅, ##STR352##
 3. A compound as claimed in claim 2, where X is methyl, phenyl or phenyl substituted by chlorine, bromine, methyl, methoxy or nitro.
 4. A compound as claimed in claim 2 where D is phenyl which is substituted by fluorine; chlorine; bromine, nitro; a carboxylic acid alkyl ester having an alkyl ester radical selected from the group consisting of C₁ -C₆ alkyl or alkoxyalkyl, phenyl and benzyl; oxodiazolyl; methyl; methoxy; ethoxy; phenylazo (which is unsubstituted or substituted by chlorine, bromine, a carboxylic acid alkyl ester having an alkyl ester radical selected from the group consisting C₁ -C₆ alkyl or alkoxyalkyl, phenyl, and benzyl, unsubstituted or unsubstituted or substituted carbamyl or sulfamyl wherein the substituent radicals are selected from the group consisting of NH₂, NHCH₃, NHC₂ H₅, NHC₃ H₇, NHC₄ H₉, ##STR353## NHCH₂ C₆ H₅, NHC₆ H₄ Cl, NHC₆ H₃ Cl₂, NHC₆ H₂ Cl₃, NHC₆ H₄ Br, NHC₆ H₄ OCH₃, HNC₆ H₄ OC₂ H₅, NHC₆ H₃ ClOCH₃, NHC₆ H₄ NHCOCH₃, NHC₆ H₄ NHCOC₆ H₅, NHNHCOC₆ H₅, NHNHCOC₆ H₄ Cl, NHNHCOC₆ H₄ CH₃, NHC₆ H₃ ClCH₃, NHC₆ H₂ Cl₂ OCH₃ and NHC₆ H₂ Cl₂ CH₃ ; or nitro); cyano; carbamyl; methyl sulfonyl; ethylsulfonyl; phenylsulfonyl; benzoyl; or acylamino selected from the group consisting of NHCOCH₃, NHCOC₂ H₅, NHCOC₃ H₇, NHCOC₆ H₅, NHCOC₆ H₄ Cl, NHCOC₆ H₄ Cl₂, NHCOC₆ H₄ Br, NHCOC₆ H₄ OCH₃, NHCOC₁₀ H₇, NHCONH₂, NHCONHC₆ H₅, ##STR354##
 5. A compound as claimed in claim 3 where D is phenyl which is substituted by fluorine; chlorine; bromine; nitro; a carboxylic acid alkyl ester having an alkyl ester radical selected from the group consisting of C₁ -C₆ alkyl or alkoxyalkyl, phenyl and benzyl; oxodiazolyl; methyl; methoxy; ethoxy; phenylazo (which is unsubstituted or substituted by chlorine, bromine, a carboxylic acid alkyl ester having an alkyl ester radical selected from the group consisting of C₁ -C₆ alkyl or alkoxyalkyl, phenyl, and benzyl; unsubstituted or substituted carbamyl or sulfamyl wherein the substituent radicals are selected from the group consisting of NH₂, NHCH₃, NHC₂ H₅, NHC₃ H₇, NHC₄ H₉, ##STR355## NHCH₂ C₆ H₅, NHC₆ H₄ Cl, NHC₆ H₃ Cl₂, NHC₆ H₂ Cl₃, NHC₆ H₄ Br, NHC₆ H₄ OCH₃, NHC₆ H₄ OC₂ H₅, NHC₆ H₃ ClOCH₃, NHC₆ H₄ NHCOCH₃, NHC₆ H₄ NHCOC₆ H₅, NHNHCOC₆ H₅, NHNHCOC₆ H₄ Cl, NHNHCOC₆ H₄ CH₃, NHC₆ H₃ ClCH₃, NHC₆ H₂ Cl₂ OCH₃ and NHC₆ H₂ Cl₂ CH₃ ; or (nitro); cyano; carbamyl; methyl sulfonyl; ethylsulfonyl; phenylsulfonyl; benzoyl or acylamino selected from the group consisting of NHCOCH₃, NHOCOC₂ H₅, NHCOC₃ H₇, NHCOC₆ H₅, NHCOC₆ H₄ Cl, NHCOC₆ H₃ Cl₂, NHCOC₆ H₄ Br, NHCOC₆ H₄ OCH₃, NHCOC₁₀ H₇, NHCOHN₂, NHCONHC₆ H₅, ##STR356## 